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CN119191285B - Graphite for friction material and preparation method and application thereof - Google Patents

Graphite for friction material and preparation method and application thereof Download PDF

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Publication number
CN119191285B
CN119191285B CN202411718117.3A CN202411718117A CN119191285B CN 119191285 B CN119191285 B CN 119191285B CN 202411718117 A CN202411718117 A CN 202411718117A CN 119191285 B CN119191285 B CN 119191285B
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graphite
friction material
parts
carbon material
iron powder
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CN119191285A (en
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王玲玉
韩雪
王颖
何思敏
臧昜
高翔
何智钢
郑安然
郝旭敏
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Tangshan Kimwan Special Carbon&graphite Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/205Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/022Carbon
    • C04B14/024Graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02Macromolecular compounds
    • C04B26/10Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/12Condensation polymers of aldehydes or ketones
    • C04B26/122Phenol-formaldehyde condensation polymers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • C04B40/0046Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/149Antislip compositions
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00362Friction materials, e.g. used as brake linings, anti-skid materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Braking Arrangements (AREA)

Abstract

The application relates to the technical field of graphite materials, and particularly discloses graphite for a friction material, a preparation method and application thereof. The graphite for the friction material comprises 10000+/-20 parts of carbon material, 4900-9900 parts of sulfuric acid, 9900-29700 parts of organic acid and 60-80 parts of filler, wherein the weight ratio of the carbon material to the organic acid to the sulfuric acid is 1 (0.99-2.97) (0.49-0.99), the carbon material is one of coke carbon material or graphite carbon material, the filler comprises 24-28 parts of modified iron powder, 12-14 parts of sodium bicarbonate powder and 30-32 parts of hole sealing agent, the organic acid is one of acetic acid, oxalic acid or citric acid, and the preparation method comprises the steps of adding the carbon material after mixing the organic acid and the sulfuric acid, mixing, washing to be neutral, drying, calcining, graphitizing, adding the sodium bicarbonate and the iron powder, uniformly mixing after adding the hole sealing agent, and uniformly mixing. The graphite for the friction material can be used for preparing the friction material, and has the advantages of improving the rebound rate of the elastic graphite and further meeting the use requirement of the friction material.

Description

Graphite for friction material and preparation method and application thereof
Technical Field
The application relates to the technical field of graphite materials, in particular to graphite for a friction material, a preparation method and application thereof.
Background
The common graphite used for friction materials is mainly artificial graphite, which is mainly formed by calcining high-quality petroleum coke or asphalt coke at a high temperature of 2500-3000 ℃, and the proper amount of artificial graphite can improve the lubricating property of the friction materials, reduce abrasion and alleviate friction force, so the artificial graphite has been widely used in brake materials.
Since graphite is rapidly oxidized when the use temperature is higher than 500 ℃, the surface of the friction material becomes loose and abrasion is increased. Therefore, in an air environment, the artificial graphite is suitable for use at medium and low temperatures, and the lubricating performance is reduced when the temperature exceeds 500 ℃. And the sensitivity of the brake pad to speed and temperature can be reduced by the elastic graphite, the friction coefficient change caused by the speed and the temperature is reduced, and the brake performance and the comfort level of a driver are improved. Therefore, the elastic graphite is used to replace the artificial graphite to be added into the friction material, so that the friction plate has the characteristics of high temperature resistance, corrosion resistance, low density and the like.
The rebound rate is used as an important factor influencing the compression performance and rebound resilience performance of the elastic graphite, and a certain gap is reserved between the rebound rate of the elastic graphite developed in China and abroad at present. In order to improve the rebound rate of the elastic graphite and reduce the production cost of the friction material, the inventor develops graphite for the friction material to replace foreign imported materials so as to meet the use requirement of the friction material.
Disclosure of Invention
The application provides graphite for a friction material, a preparation method and application thereof in order to improve the rebound rate of elastic graphite and further meet the use requirement of the friction material.
In a first aspect, the present application provides a graphite for a friction material, which adopts the following technical scheme:
The graphite for the friction material comprises the following raw materials in parts by weight:
10000+/-20 parts of carbon material, 4900-9900 parts of sulfuric acid, 9900-29700 parts of organic acid and 60-80 parts of filler;
wherein the weight ratio of the carbon material to the organic acid to the sulfuric acid is 1 (0.99-2.97): 0.49-0.99);
the carbon material is one of a coke-based carbon material or a graphite-based carbon material;
The filler comprises 24-28 parts of modified iron powder, 12-14 parts of sodium bicarbonate powder and 30-32 parts of hole sealing agent;
The organic acid is one of acetic acid, oxalic acid or citric acid.
According to the technical scheme, the elastic graphite is prepared by blending the carbon material with the high-concentration organic acid and sulfuric acid, so that sulfuric acid reacts with the carbon material and fills sulfur into the carbon material, the organic acid can promote the reaction to be carried out and is convenient for separating generated reaction products from the carbon material when adjusting the pH value in a reaction system, the possibility of impurity residue in the carbon material is reduced, the graphitized sulfur generates gas and is separated from the carbon material, the carbon material forms the elastic graphite, the filler is filled in the air holes of the upper opening of the elastic graphite, sodium bicarbonate and modified iron powder are positioned in the air holes at the moment, and the hole sealing agent seals the opening of the air holes, so that the rebound rate of the prepared elastic graphite is improved, and the use requirement of the friction material is met.
Preferably, the modified iron powder is prepared by wrapping sodium polyacrylate with iron powder, and the weight ratio of the iron powder to the sodium polyacrylate is (3-5): 1.
According to the technical scheme, when the weight ratio of the iron powder to the sodium polyacrylate is in the range, the sodium polyacrylate is wrapped on the surface of the iron powder, the possibility of mutual contact and agglomeration between the iron powder is reduced, the dispersibility of the iron powder is improved, when the iron powder is filled in the air holes of the elastic graphite, the sodium polyacrylate reduces the possibility of sedimentation of the iron powder, so that the iron powder is uniformly distributed in the air holes all the time, when the ratio of the iron powder to the sodium polyacrylate is larger than the range, the sodium polyacrylate is difficult to fully wrap the iron powder, the possibility of the iron powder being difficult to fully disperse and agglomerate is easily caused, and when the ratio of the iron powder to the sodium polyacrylate is smaller than the range, the possibility of raw material waste is easily caused, and further the production cost is adversely affected.
Preferably, the hole sealing agent is prepared by adsorbing asphalt-based aluminum paste by graphene aerogel, wherein the weight ratio of the graphene aerogel to the asphalt-based aluminum paste is 1 (10-12).
Through adopting above-mentioned technical scheme, when graphite alkene aerogel and through the mode of graphite alkene aerogel physical adsorption pitch base aluminium thick liquid, be convenient for evenly disperse pitch base aluminium thick liquid, and fill pitch base aluminium thick liquid in the gas pocket of elasticity graphite, because the high elastic characteristics of graphite alkene aerogel self, and then improve the resilience rate of the elasticity graphite that makes, and when preparing friction material through elasticity graphite, graphite alkene aerogel extrudes inside pitch base aluminium thick liquid under the condition of hot pressing, the opening of the gas pocket on the shutoff elasticity graphite of being convenient for, further be convenient for form closed micropore on the elasticity graphite, improve the resilience rate of elasticity graphite, satisfy friction material's user demand.
Preferably, the preparation method of the hole sealing agent comprises the following steps:
freezing and molding asphalt-based aluminum paste to obtain molded solid;
Crushing the formed solid to prepare particles;
Adding graphene aerogel into the prepared particles according to the weight ratio, and performing ultrasonic dispersion to obtain the hole sealing agent.
Through adopting above-mentioned technical scheme, through the mode with pitch base aluminium thick liquid freeze molding and broken for pitch base aluminium thick liquid forms the solid that viscosity is less and easily by graphene aerogel physical adsorption, and through the granule of ultrasonic dispersion's mode intensive mixing graphene aerogel and pitch base aluminium thick liquid, the pitch base aluminium thick liquid granule of being convenient for is filled in the hole of graphene aerogel, and the hole of being convenient for fully dispersed pitch base aluminium thick liquid, and then filling elastic graphite.
Preferably, the particle size of the sodium bicarbonate powder is 140-160nm.
According to the technical scheme, when the particle size of sodium bicarbonate powder is in the range, sodium bicarbonate powder is easy to fill pores on elastic graphite, sodium carbonate, carbon dioxide gas and water are generated when the sodium bicarbonate powder is heated and decomposed, micropores are formed on the surface of the sodium bicarbonate powder easily, the sodium carbonate is further decomposed and releases carbon dioxide gas in a heated environment, micropores are further formed on the surface of the sodium carbonate, the generated carbon dioxide gas enters graphene aerogel, asphalt-based aluminum paste is extruded and plugs the pore openings of the elastic graphite, the number of closed micropores in the elastic graphite is increased, the generated water reacts with iron powder under the heated environment to generate ferroferric oxide and produce volume expansion, so that a ferroferric oxide skeleton is formed, the elastic graphite is supported while the closed micropores in the elastic graphite are increased, the adverse influence on the strength of the elastic graphite is reduced, the use requirement of friction materials is met, when the particle size of the sodium bicarbonate powder is too large, the sodium bicarbonate powder is difficult to enter the pores of the elastic graphite easily, when the particle size of the sodium bicarbonate powder is too small, the sodium bicarbonate powder is easy to agglomerate and difficult to fully disperse easily, the sodium bicarbonate powder is easy to cause agglomeration and difficult to enter the pores of the elastic graphite easily, and the elastic graphite is difficult to influence the elastic graphite is difficult to rebound, and the elastic graphite is difficult to enter the elastic graphite.
In a second aspect, the application provides a preparation method of graphite for friction materials, which adopts the following technical scheme:
A preparation method of graphite for friction materials comprises the following steps:
mixing organic acid and sulfuric acid according to the weight ratio, adding a carbon material, and mixing for 20-60min at 40-80 ℃;
Washing the prepared mixture to be neutral, and drying to prepare a dried carbon material;
calcining the dried carbon material at 600+/-10 ℃ for 12+/-4 hours, and graphitizing the calcined carbon material for 36+/-1 hour to prepare graphitized elastic graphite;
Uniformly mixing sodium bicarbonate powder and modified iron powder according to a weight ratio, adding the mixture into graphitized elastic graphite, and uniformly mixing to obtain a mixture;
and adding the hole sealing agent into the mixture, and uniformly mixing to obtain the graphite for the friction material.
Through adopting above-mentioned technical scheme, sulfuric acid reacts with the carbon material, the organic acid adjusts pH in reaction system and promotes the reaction to go on, thereby introduce the sulfur element into the carbon material, the carbon material of introducing the sulfur element is through washing, the stoving, calcination, graphitization back sulfur element changes sulfur dioxide loss, the carbon material changes into elastic graphite, at this moment, mix sodium bicarbonate powder and modified iron powder and fill elastic graphite hole, modified iron powder reduces sodium bicarbonate powder subsidence's possibility, thereby make sodium bicarbonate surface's micropore evenly distributed in elastic graphite, fill hole sealing agent in elastic graphite's hole and shutoff drill way, further increase elastic graphite's closed micropore's quantity, when the graphite for friction material that will prepare is applied to the friction material, the hole sealing agent makes the inside closed micropore's of graphite increase of friction material, and then increase the resilience rate of graphite for friction material, and when the friction material that prepares is used, the friction material is heated thereby make the sodium bicarbonate decompose, thereby further make the closed micropore's in the friction material increase in quantity, and the iron powder that is close to in the friction material generates ferroferric oxide and expands in volume, improve the intensity of the friction material's that is close to the surface of friction material, the iron powder is formed by the oxidation material can further be satisfied by the oxidation demand of oxidation material, can be further reduced in the friction material.
Preferably, the graphitization temperature is 2000-2800 ℃.
By adopting the technical scheme, when the graphitization temperature is in the range, the graphitization degree of the carbon material is gradually increased along with the temperature rise, the rearrangement of carbon atoms is promoted, a more ordered graphite structure is formed, the thermal conductivity and the mechanical property are both increased, when the graphitization temperature is less than the range, the possibility of incomplete graphitization is easily caused, the rebound rate of graphite for the friction material is influenced, and when the graphitization temperature exceeds the range, the possibility of cracking and damage of the graphite for the friction material is easily caused, and the mechanical property of the prepared friction material is further adversely affected.
In a third aspect, the application provides an application of graphite for friction materials, which adopts the following technical scheme:
a friction material made using graphite for the friction material, comprising the steps of:
Uniformly mixing reinforcing fibers, steel fibers, fillers, phenolic resin and graphite for the friction material, adding the uniformly mixed raw materials into a pressing die, and hot-pressing and molding at the hot-pressing temperature of 160+/-10 ℃ and the pressure of 30+/-1 MPa to obtain the friction material.
Through adopting above-mentioned technical scheme, the graphite for friction material that will prepare is applied to in the friction material through hot pressing method, in being convenient for extrude the graphite aerogel with pitch base aluminium thick liquid, the gas pocket opening of the graphite for the shutoff membrane material of being convenient for improves the resilience rate of the graphite for the friction material, satisfies the user demand of friction material.
In summary, the application has the following beneficial effects:
1. filling filler into the air holes of the upper opening of the elastic graphite, wherein sodium bicarbonate and iron powder are positioned in the air holes, and the hole sealing agent seals the air holes, so that the quantity of closed micropores on the elastic graphite is increased, the rebound rate of the prepared elastic graphite is further increased, and the use requirement of friction materials is further met.
2. Through the mode of graphite alkene aerogel physical adsorption pitch base aluminium thick liquid, be convenient for evenly disperse pitch base aluminium thick liquid, and fill pitch base aluminium thick liquid in the gas pocket of elasticity graphite, because the high elasticity's of graphite alkene aerogel self characteristics, can improve the resilience rate of the elasticity graphite that makes when filling graphite alkene aerogel in the gas pocket, and when preparing friction material through elasticity graphite, graphite alkene aerogel extrudes inside pitch base aluminium thick liquid under the condition of hot pressing, the opening of the gas pocket on the shutoff elasticity graphite of being convenient for, further be convenient for form closed micropore on the elasticity graphite, improve the resilience rate of elasticity graphite, satisfy friction material's user demand.
3. When the particle size of the sodium bicarbonate powder is within the range, the sodium bicarbonate powder is easy to fill the air holes on the elastic graphite, sodium carbonate, carbon dioxide gas and water are generated when the sodium bicarbonate powder is heated and decomposed, micropores are easily formed on the surface of the sodium bicarbonate, the sodium carbonate is further decomposed and released in a heated environment, micropores are further formed on the surface of the sodium carbonate, so that the number of closed micropores in the elastic graphite is increased, the generated water reacts with iron powder in the heated environment to generate ferroferric oxide and generate volume expansion, a ferroferric oxide framework is formed, the elastic graphite is supported while the closed micropores in the elastic graphite are increased, adverse effects on the strength of the elastic graphite are reduced, and the use requirement of friction materials is met.
Detailed Description
The present application will be described in further detail with reference to examples.
The rebound rate detection method and the initial oxidation temperature detection method in all examples and comparative examples are as follows:
1. Rebound rate
The test equipment is a material testing machine which can uniformly apply load and has the load measurement precision of +/-1 percent.
Sample 5 groups of samples were taken, each group of samples being 3 copies.
Filling a sample into a mould with an inner diameter of 40mm until the initial height of the sample in the mould is 8.0mm (three points are measured at equal intervals, an arithmetic average value is taken), placing a top plug matched with the mould on the upper side of the sample, placing the mould with the upper end for plugging the plug between a pressure head and a base, enabling the load to apply initial load to 0.35MPa at constant speed through the axis of the pressure head, recording deformation after 15s, loading to 35MPa at constant speed within 10s, recording final load deformation after 60s, unloading to initial load, and recording deformation after 60 s.
Test results and calculations:
wherein R is rebound rate,%;
t 1 -initial load deflection, mm;
T 2 -final load deflection, mm;
t 3 -unloading to the deformation under initial load, mm.
2. Initial oxidation temperature
Test equipment:
The thermobalance is zero position type or deflection type. When the mass of the sample is less than 50mg, the precision is +/-0.020 mg. The thermal balance is constructed so that the air flow is around the sample and so that heat is transferred to the sample at a constant rate.
The furnace body is provided with a shell with low heat capacity, and can be heated and cooled rapidly or slowly (generally at a speed of at least 50 ℃ per minute) in a temperature range from room temperature to 1200 ℃.
And a temperature sensor for measuring the temperature of the sample. Is located as close to the sample as possible.
The temperature-raising program controller can perform linear rate scanning within a preset temperature range.
Recording means for displaying the mass loss versus temperature or time and recording the mass of the sample and the change in temperature and/or time.
The sample dish is of a shape and size sufficient to carry 10mg of sample and is made of a material that can withstand the highest use temperatures.
The protective gas is dry air, and the water content is less than 0.001% (mass fraction).
The flow meter measures the gas flow rate in the range of 50mL/min to 150 mL/min.
Balance the initial mass of the test sample was measured with an accuracy of 0.01mg.
Sample 5 groups of samples, 10mg each.
Sample step:
And zeroing the thermal balance, placing the weighed sample in a sample dish, placing the sample dish containing the sample on the thermal balance, selecting the gas flow rate, introducing the gas flow and recording the initial mass. The instrument was started and the temperature was raised to 1050℃at a rate of 100℃per minute.
And (3) the sample results show thermogravimetric data in the form of a mass change amount and temperature relation curve, and the initial oxidation temperature of the sample is determined.
Raw materials
The starting materials used in the preparation examples and examples of the present application are commercially available. Wherein the concentration of sulfuric acid is 98%, the concentration of organic acid is 99%, and the iron powder, sodium polyacrylate, graphene aerogel and sodium bicarbonate powder are all nano-scale particles.
Preparation example
Preparation example 1 modified iron powder
PREPARATION EXAMPLE 1.1
A modified iron powder is prepared by the following steps:
75g of iron powder and 25g of sodium polyacrylate are uniformly mixed to prepare modified iron powder.
PREPARATION EXAMPLE 1.2
Unlike preparation example 1.1, the iron powder addition amount in preparation example 1.2 was 80g and the sodium polyacrylate addition amount was 20g.
PREPARATION EXAMPLE 1.3
Unlike preparation example 1.1, the amount of iron powder added in preparation example 1.3 was 86g, and the amount of sodium polyacrylate added was 14g.
PREPARATION EXAMPLE 1.4
Unlike preparation example 1.1, the iron powder was added in an amount of 50g and the sodium polyacrylate was added in an amount of 50g in preparation example 1.4.
PREPARATION EXAMPLE 1.5
Unlike preparation example 1.1, the amount of iron powder added in preparation example 1.5 was 90g, and the amount of sodium polyacrylate added was 10g.
PREPARATION EXAMPLE 1.6
Unlike preparation example 1.2, sodium polyacrylate was replaced with sodium silicate in equal amount in preparation example 1.6.
PREPARATION EXAMPLE 1.7
Unlike preparation example 1.2, sodium polyacrylate was replaced with fumed silica in the same amount in preparation example 1.7.
Preparation example 2 hole sealing agent
PREPARATION EXAMPLE 2.1
A hole sealing agent is prepared by the following steps:
freezing and molding 109g of asphalt-based aluminum paste to obtain molded solid;
Crushing the formed solid to prepare particles;
and adding 11g of graphene aerogel into the prepared particles, and performing ultrasonic dispersion to prepare the hole sealing agent.
PREPARATION EXAMPLE 2.2
Unlike preparation example 2.1, the addition amount of the asphalt-based aluminum paste in preparation example 2.2 was 110g, and the addition amount of the graphene aerogel was 10g.
PREPARATION EXAMPLE 2.3
Unlike preparation example 2.1, the addition amount of the asphalt-based aluminum paste in preparation example 2.3 was 111g, and the addition amount of the graphene aerogel was 9g.
PREPARATION EXAMPLE 2.4
Unlike preparation example 2.1, the addition amount of the asphalt-based aluminum paste in preparation example 2.4 was 114g, and the addition amount of the graphene aerogel was 6g.
PREPARATION EXAMPLE 2.5
Unlike preparation example 2.1, the addition amount of the asphalt-based aluminum paste in preparation example 2.5 was 100g, and the addition amount of the graphene aerogel was 20g.
PREPARATION EXAMPLE 2.6
Unlike preparation example 2.2, the graphene aerogel was replaced with activated carbon in equal amount in preparation example 2.6.
PREPARATION EXAMPLE 2.7
Unlike preparation example 2.2, the pitch-based aluminum paste was replaced with a silicon aluminum resin in the same amount in preparation example 2.7.
Examples
Example 1 raw material ratios and Process parameters
Example 1.1
Graphite for friction material, which is prepared by the following steps:
After 9900g of acetic acid and 9900g of sulfuric acid were mixed, 10000g of coke was added and mixed at 40 ℃ for 20min;
Washing the prepared mixture to be neutral, and drying to prepare a dried carbon material;
calcining the dried carbon material for 12 hours at 600 ℃, and graphitizing the calcined carbon material for 36 hours at 2000 ℃ to obtain graphitized elastic graphite;
uniformly mixing 12g of sodium bicarbonate powder with the particle size of 140nm and 28g of modified iron powder from preparation example 1.1, adding the mixture into graphitized elastic graphite, and uniformly mixing to prepare a mixture;
30g of the sealing agent from preparation example 2.1 was added to the mixture and mixed uniformly to prepare graphite for friction material.
Examples 1.2 to 1.7
Unlike example 1.1, the raw material ratios and process parameters in examples 1.2-1.7 are different and are detailed in Table 1.
Table 1 examples 1.1-1.7 raw material ratios and process parameters
Example 1.8
Unlike example 1.6, the coke was replaced with an equal amount of graphite in example 1.8.
Example 1.9
Unlike example 1.8, acetic acid was replaced with an equal amount of oxalic acid in example 1.9.
Example 1.10
Unlike example 1.8, acetic acid was replaced with an equal amount of citric acid in example 1.10.
Comparative example 1
Unlike example 1.1, comparative example 1 uses an equivalent amount of iron powder instead of the modified iron powder.
Comparative example 2
Unlike example 1.1, comparative example 2 replaced sodium bicarbonate powder with an equal amount of sodium carbonate powder.
Comparative example 3
Unlike example 1.1, comparative example 3 replaces sodium bicarbonate powder with an equal amount of calcium carbonate powder.
The graphite used for friction materials prepared in examples 1.1 to 1.10 and comparative examples 1 to 3 was examined for rebound rate and initial oxidation temperature, and is shown in Table 2.
Table 2 table of performance test data
As can be seen from the combination of tables 1 and 2, the graphite for friction material prepared in examples 1.1 to 1.10 exhibited better rebound rate and initial oxidation temperature than those of comparative example 1, which demonstrates that the modified iron powder used in examples 1.1 to 1.10 of the present application is advantageous in improving rebound rate and initial oxidation temperature of the graphite for friction material prepared.
As a result of combining example 1.1 with comparative examples 2 to 3, it was found that comparative example 2, in which sodium carbonate was used in an equivalent amount to replace sodium bicarbonate, produced graphite for friction material exhibited inferior to example 1.1 in both rebound rate and initial oxidation temperature, and comparative example 3, in which calcium carbonate was used in an equivalent amount to replace sodium bicarbonate, produced graphite for friction material exhibited inferior to example 1.1 in both rebound rate and initial oxidation temperature, which means that sodium bicarbonate selected in example 1.1 was advantageous in improving rebound rate and initial oxidation temperature of graphite for friction material produced.
The effect of the addition amounts of acetic acid and sulfuric acid was examined in examples 1.1 to 1.3, and as a result, it was found that the graphite for friction material produced in example 1.2 exhibited better in terms of rebound rate and initial oxidation temperature, probably because the addition amounts of acetic acid and sulfuric acid selected in example 1.2 caused the reaction of sulfuric acid with carbon material to be promoted, so that the carbon material was filled with a proper amount of sulfur element, and the graphitization degree of the carbon material was improved, and the rebound rate of the graphite for friction material produced was improved.
Taking example 1.2 as a control, examples 1.4 to 1.5 examined the effects of the mixing temperature, mixing time and graphitization temperature, and found that the graphite for friction material prepared in example 1.4 exhibited better in terms of rebound rate and initial oxidation temperature, which indicated that the mixing temperature, mixing time and graphitization temperature selected in example 1.4 were favorable for increasing the rebound rate and initial oxidation temperature of the graphite for friction material prepared.
Taking example 1.4 as a control, the influence of the filler ratio was examined in examples 1.6 to 1.7, and as a result, it was found that the graphite for friction material produced in example 1.6 exhibited better in terms of rebound rate and initial oxidation temperature, which means that the filler ratio selected in example 1.6 was favorable for improving the rebound rate and initial oxidation temperature of the graphite for friction material produced.
Taking example 1.6 as a control, and examining the influence of different carbon materials in example 1.8, it is found that the graphite used for the friction material prepared in example 1.8 is better in rebound rate and initial oxidation temperature by replacing coke with an equal amount of graphite, which indicates that the carbon material is selected as the graphite, so that the rebound rate and initial oxidation temperature of the graphite used for the friction material prepared are improved.
As a result of examining the influence of different organic acids in examples 1.9 to 1.10 by taking example 1.8 as a control, it was found that the graphite for friction material prepared in example 1.10 exhibited better in rebound rate and initial oxidation temperature, which means that the use of citric acid as the organic acid was favorable for improving the rebound rate and initial oxidation temperature of the graphite for friction material prepared.
EXAMPLE 2 sodium bicarbonate powder particle size
Example 2.1
Unlike example 1.10, the particle size of the sodium bicarbonate powder in example 2.1 was 150nm.
Example 2.2
Unlike example 1.10, the particle size of the sodium bicarbonate powder in example 2.2 was 160nm.
Example 2.3
Unlike example 2.1, the particle size of the sodium bicarbonate powder in example 2.3 was 100nm.
Example 2.4
Unlike example 2.1, the particle size of the sodium bicarbonate powder in example 2.4 was 200nm.
The graphite used for friction materials prepared in examples 2.1-2.4 was tested for rebound rate and initial oxidation temperature as detailed in Table 3.
Table 3 table of performance test data
As can be seen from the combination of Table 3, taking example 1.10 as a control, examples 2.1 to 2.4 examined the effect of the particle size of sodium bicarbonate, and as a result, it was found that the graphite for friction material obtained in example 2.1 exhibited better in terms of rebound rate and initial oxidation temperature, which means that the particle size of sodium bicarbonate powder selected in example 2.1 was favorable for improving the rebound rate and initial oxidation temperature of the graphite for friction material obtained.
EXAMPLE 3 modified iron powder
Examples 3.1 to 3.6
Unlike example 2.1, the modified iron powders in examples 3.1 to 3.6 are derived from preparation examples 1.2 to 1.7 in equal amounts.
The graphite used for friction materials prepared in examples 3.1-3.6 was tested for rebound rate and initial oxidation temperature as detailed in Table 4.
Table 4 table of performance test data
As can be seen from table 4, taking example 2.1 as a control, examples 3.1 to 3.4 examined the influence of the proportion of the modified iron powder, and as a result, it was found that the graphite for friction material prepared in example 3.1 exhibited better in terms of rebound rate and initial oxidation temperature, which means that the proportion of the modified iron powder selected in example 3.1 was favorable for improving the rebound rate and initial oxidation temperature of the graphite for friction material prepared.
Taking example 3.1 as a control, example 3.5 replaces sodium polyacrylate with equal amount of sodium silicate, example 3.6 replaces sodium polyacrylate with equal amount of fumed silica, and the prepared graphite for the friction material has poorer rebound rate and initial oxidation temperature than example 3.1, which shows that the compounding of sodium polyacrylate and iron powder in example 3.1 is beneficial to improving the rebound rate and initial oxidation temperature of the prepared graphite for the friction material.
Example 4 hole sealing agent
Examples 4.1 to 4.6
Unlike example 3.1, the same amounts of sealer in examples 4.1-4.6 were from preparations 2.2-2.7.
The graphite used for friction materials prepared in examples 4.1 to 4.6 was tested for rebound rate and initial oxidation temperature as shown in Table 5.
Table 5 table of performance test data
As can be seen from table 5, taking example 3.1 as a control, examples 4.1 to 4.4 examined the effect of the ratio of the pore sealing agent, and as a result, it was found that the graphite for friction material prepared in example 4.1 exhibited better in terms of rebound rate and initial oxidation temperature, which means that the ratio of the pore sealing agent selected in example 4.1 was favorable for improving the rebound rate and initial oxidation temperature of the graphite for friction material prepared.
In comparison with example 4.1, in example 4.5, the graphene aerogel is replaced by the same amount of activated carbon, in example 4.6, the asphalt-based aluminum paste is replaced by the same amount of silicon-aluminum resin, and the prepared graphite for the friction material has a lower rebound rate and initial oxidation temperature than those of example 4.1, which means that the combination of the graphene aerogel and the asphalt-based aluminum paste in example 4.1 is beneficial to improving the rebound rate and initial oxidation temperature of the prepared graphite for the friction material.
The volatile matter and sulfur content of the graphite for friction materials prepared in examples 1 to 4 were measured according to the detection method of national standard GB/T3521-2023 "graphite chemistry analysis method". As a result, the graphite used for the friction material prepared in examples 1-4 has the volatile content of less than 0.5%, the sulfur content of less than 0.5%, and the graphitization degree of 70-90, and meets the use requirements of the friction material.
Application example 1
A friction material made by the steps of:
uniformly mixing reinforcing fibers, steel fibers, fillers, phenolic resin and graphite for the friction material, adding the uniformly mixed raw materials into a pressing die, and hot-pressing and molding at the hot-pressing temperature of 160 ℃ and the pressure of 30MPa to obtain the friction material.
Application examples 2 to 26
Unlike application example 1, the graphite for friction material in application examples 2 to 26 was equally derived from examples 1 to 4, respectively.
Comparative application examples 1 to 3
Unlike application example 1, the graphite for friction material in comparative application examples 1 to 3 was derived from comparative examples 1 to 3 in equal amounts, respectively.
Performance test
The following performance test experiments were conducted for the friction materials prepared in application examples 1 to 26 and comparative application examples 1 to 3. Performance testing experiments included shear strength, impact strength, density, wear rate, and compression strain rate of the friction material. The test data are shown in Table 6.
1. Shear strength
The shear strength of the friction material is detected according to the detection method of national standard GB/T22309-2023 test method for the shear strength of disc brake pad assemblies and drum brake shoe assemblies of brake linings of road vehicles. The detection temperature is 23+/-5 ℃.
2. Impact Strength
The shear strength of the friction material is detected according to the detection method of national standard GB/T33835-2017 impact strength test method of friction material. The detection temperature is 23+/-5 ℃.
3. Density of
The density of the friction material is detected according to the detection method of national standard JC/T685-2009 friction material density test method.
4. Wear rate
And detecting the abrasion loss of the friction material according to the detection method of national standard GB/T17469-2012 test method for evaluating the friction performance of the automobile brake lining, and further calculating the abrasion loss rate. The detection temperature is 350 ℃.
Compression strain rate
The compression amount of the friction material is detected according to the detection method of national standard GB/T22311-2023 compression strain test method of road vehicle brake lining, and then the compression strain rate is calculated. The detection temperature is 400 ℃.
TABLE 6 Performance test data sheets for application examples 1-26 and comparative application examples 1-3
The present application will be described in detail below with reference to the detection data provided in table 6.
In combination with comparative examples 1 to 3 and examples 1 to 26, it was found that the friction materials of examples 1 to 26 of the present application exhibited better properties in terms of shear strength, impact strength, wear rate and compression strain rate than the friction materials of comparative examples 1 to 3, and the densities were smaller than the friction materials of comparative examples 1 to 3, indicating that the graphite for friction materials of the present application exhibited better properties in terms of improving the shear strength and impact strength of the friction materials while reducing the density, wear rate and compression strain rate of the friction materials.
It was found that the modified iron powder was replaced with the same amount of iron powder in comparative application example 1 in combination with application example 1 and comparative application examples 1 to produce a friction material having inferior properties in terms of shear strength, impact strength, density, wear rate and compression strain rate to application example 1, which means that the modified iron powder selected in application example 1 of the present application is advantageous in reducing the density, wear rate and compression strain rate of the friction material while improving the shear strength and impact strength of the produced friction material.
The comparative application example 2 in which sodium carbonate was replaced with an equal amount of sodium carbonate gave a friction material having inferior properties in terms of shear strength, impact strength, density, wear rate and compression strain rate to application example 1, which indicates that the sodium bicarbonate selected in application example 1 of the present application is advantageous in reducing the density, wear rate and compression strain rate of the friction material while improving the shear strength and impact strength of the friction material.
The comparative application example 3, in which the equivalent amount of calcium carbonate was used instead of sodium bicarbonate, produced friction materials were inferior to application example 1 in terms of shear strength, impact strength, density, wear rate and compression strain rate, which means that the sodium bicarbonate selected in application example 1 of the present application is advantageous in reducing the density, wear rate and compression strain rate of the friction materials while improving the shear strength and impact strength of the produced friction materials.
As a result of examining the influence of the addition amount of acetic acid and the addition amount of sulfuric acid in application examples 1 to 3, it was found that the friction material produced in application example 2 exhibited better in terms of shear strength, impact strength, wear rate and compression strain rate and had a smaller density, which means that the addition amount of acetic acid and the addition amount of sulfuric acid selected in application example 2 were more advantageous in reducing the density, wear rate and compression strain rate of the friction material while improving the shear strength and impact strength of the produced friction material.
Taking application example 2 as a control, the influences of mixing time, mixing temperature and graphitization temperature are examined in application examples 4-5, and as a result, it is found that the friction material prepared in application example 4 is better in terms of shear strength, impact strength, wear rate and compression strain rate and is smaller in density, which means that the mixing time, mixing temperature and graphitization temperature selected in application example 4 are more favorable for reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
Taking application example 4 as a comparison, the influence of the filler ratio is examined in application examples 6-7, and as a result, the friction material prepared in application example 6 is found to be better in terms of shear strength, impact strength, wear rate and compression strain rate and smaller in density, which means that the filler ratio selected in application example 6 is more favorable for reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
Taking application example 6 as a comparison, application example 8 examines the influence of different carbon materials, and as a result, application example 8 finds that the same amount of graphite is used for replacing coke, and the prepared friction material is better in terms of shear strength, impact strength, wear rate and compression strain rate and is smaller in density, which shows that the preferable graphite is the carbon material, so that the density, wear rate and compression strain rate of the friction material are better reduced, and meanwhile, the shear strength and impact strength of the prepared friction material are improved.
Taking application example 8 as a comparison, application examples 9-10 examine the influence of different organic acids, and as a result, it is found that the application example 10 selects citric acid to replace acetic acid, and the prepared friction material is better in terms of shear strength, impact strength, wear rate and compression strain rate and is smaller in density, which shows that the preferential selection of citric acid as the organic acid is more beneficial to reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
Taking application example 10 as a control, the influence of the particle size of sodium bicarbonate was examined in application examples 11 to 14, and as a result, it was found that the friction material produced in application example 11 exhibited better in terms of shear strength, impact strength, wear rate and compression strain rate and had a smaller density, which means that the particle size of sodium bicarbonate selected in application example 11 was more favorable for reducing the density, wear rate and compression strain rate of the friction material while improving the shear strength and impact strength of the produced friction material.
Taking application example 11 as a comparison, the influence of the proportion of the modified iron powder is examined in application examples 15-18, and as a result, the friction material prepared in application example 15 is found to be better in terms of shear strength, impact strength, wear rate and compression strain rate and smaller in density, which means that the proportion of the modified iron powder selected in application example 15 is more favorable for reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
In the case of application example 15 as a control, the equivalent amount of sodium silicate is used for replacing sodium polyacrylate in application example 19, the prepared friction material has poorer performances in terms of shear strength, impact strength, density, wear rate and compression strain rate than application example 15, and the equivalent amount of fumed silica is used for replacing sodium polyacrylate in application example 20, the prepared friction material has poorer performances in terms of shear strength, impact strength, density, wear rate and compression strain rate than application example 15, which indicates that the sodium polyacrylate selected in application example 15 is beneficial to reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
Taking application example 15 as a comparison, the influence of the proportion of the hole sealing agent is examined in application examples 21-24, and as a result, the friction material prepared in application example 21 is found to be better in terms of shear strength, impact strength, wear rate and compression strain rate and smaller in density, which means that the proportion of the hole sealing agent selected in application example 21 is more favorable for reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
In comparison with application example 21, the application example 25 uses the same amount of activated carbon to replace graphene aerogel, and the prepared friction material has poorer performances in terms of shear strength, impact strength, wear rate and compression strain rate than application example 21, which indicates that the graphene aerogel selected in application example 21 is beneficial to reducing the density, wear rate and compression strain rate of the friction material and improving the shear strength and impact strength of the prepared friction material.
In the application example 21 as a control, the same amount of the silicon-aluminum resin is used for replacing the asphalt-based aluminum paste in the application example 26, and the prepared friction material has poorer performances in terms of shear strength, impact strength, density, wear rate and compression strain rate than the application example 21, which shows that the asphalt-based aluminum paste selected in the application example 21 is beneficial to reducing the density, the wear rate and the compression strain rate of the friction material and improving the shear strength and the impact strength of the prepared friction material.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (8)

1.一种摩擦材料用石墨,其特征在于,包括以下重量份的原料:1. A graphite for friction material, characterized by comprising the following raw materials in parts by weight: 碳材料10000±20份、硫酸4900-9900份、有机酸9900-29700份、填料60-80份;10000±20 parts of carbon material, 4900-9900 parts of sulfuric acid, 9900-29700 parts of organic acid, 60-80 parts of filler; 其中碳材料、有机酸和硫酸的重量比为1:(0.99-2.97):(0.49-0.99);The weight ratio of carbon material, organic acid and sulfuric acid is 1: (0.99-2.97): (0.49-0.99); 碳材料为焦炭类碳材料或石墨类碳材料中的一种;The carbon material is one of a coke-type carbon material or a graphite-type carbon material; 所述填料包括改性铁粉24-28份、碳酸氢钠粉末12-14份和封孔剂30-32份;The filler comprises 24-28 parts of modified iron powder, 12-14 parts of sodium bicarbonate powder and 30-32 parts of sealing agent; 所述有机酸为乙酸、草酸或柠檬酸中的一种。The organic acid is one of acetic acid, oxalic acid or citric acid. 2.根据权利要求1所述的一种摩擦材料用石墨,其特征在于:所述改性铁粉由铁粉包裹聚丙烯酸钠制得,所述铁粉和聚丙烯酸钠的重量比为(3-5):1。2. The graphite for friction material according to claim 1, characterized in that the modified iron powder is made by wrapping sodium polyacrylate with iron powder, and the weight ratio of the iron powder to sodium polyacrylate is (3-5):1. 3.根据权利要求1所述的一种摩擦材料用石墨,其特征在于:所述封孔剂由石墨烯气凝胶吸附沥青基铝浆制得,石墨烯气凝胶和沥青基铝浆的重量比为1:(10-12)。3. The graphite for friction material according to claim 1 is characterized in that: the sealing agent is prepared by graphene aerogel adsorbing asphalt-based aluminum paste, and the weight ratio of graphene aerogel to asphalt-based aluminum paste is 1: (10-12). 4.根据权利要求3所述的一种摩擦材料用石墨,其特征在于:所述封孔剂的制备方法为:4. The graphite for friction material according to claim 3, characterized in that: the preparation method of the sealing agent is: 将沥青基铝浆冷冻成型,得到成型后的固体;Freeze-forming the asphalt-based aluminum slurry to obtain a formed solid; 对成型后的固体进行粉碎,制得颗粒;The formed solid is crushed to obtain particles; 按重量比将石墨烯气凝胶加入制得的颗粒中超声分散,制得封孔剂。The graphene aerogel is added to the prepared particles according to a weight ratio and ultrasonically dispersed to prepare a sealing agent. 5.根据权利要求3所述的一种摩擦材料用石墨,其特征在于:所述碳酸氢钠粉末的粒径为140-160nm。5. The graphite for friction material according to claim 3, characterized in that the particle size of the sodium bicarbonate powder is 140-160 nm. 6.一种权利要求1-5任一所述的摩擦材料用石墨的制备方法,其特征在于,包括以下步骤:6. A method for preparing graphite for friction material according to any one of claims 1 to 5, characterized in that it comprises the following steps: 按重量比混合有机酸和硫酸后,加入碳材料,在40-80℃下混合20-60min;After mixing the organic acid and sulfuric acid according to the weight ratio, add the carbon material and mix at 40-80°C for 20-60 minutes; 将制得的混合物洗涤至中性,烘干,制得烘干后的碳材料;Washing the obtained mixture until it is neutral, and drying it to obtain a dried carbon material; 烘干后的碳材料在600±10℃下煅烧12±4h,煅烧后的碳材料石墨化36±1h,制得石墨化后的弹性石墨;The dried carbon material is calcined at 600±10° C. for 12±4 h, and the calcined carbon material is graphitized for 36±1 h to obtain graphitized elastic graphite; 按重量比将碳酸氢钠粉末和改性铁粉混匀加入石墨化后的弹性石墨中并混匀,制得混合料;Mixing sodium bicarbonate powder and modified iron powder according to weight ratio, adding into graphitized elastic graphite and mixing well to prepare a mixture; 将封孔剂加入混合料中混匀,制得摩擦材料用石墨。The sealing agent is added into the mixture and mixed evenly to obtain graphite for friction material. 7.根据权利要求6所述的一种摩擦材料用石墨的制备方法,其特征在于:所述石墨化温度为2000-2800℃。7. The method for preparing graphite for friction material according to claim 6, characterized in that the graphitization temperature is 2000-2800°C. 8.一种使用权利要求1-5任一所述的摩擦材料用石墨制得的摩擦材料,其特征在于,包括以下步骤:8. A friction material made of the graphite for friction material according to any one of claims 1 to 5, characterized in that it comprises the following steps: 将增强纤维、钢纤维、填料、酚醛树脂、摩擦材料用石墨混匀,将混匀的原料加入压模中在热压温度160±10℃,压力30±1MPa下热压成型,制得摩擦材料。The reinforcing fiber, steel fiber, filler, phenolic resin and friction material graphite are mixed evenly, the mixed raw materials are added into a pressing mold, and hot pressing is performed at a hot pressing temperature of 160±10° C. and a pressure of 30±1 MPa to obtain the friction material.
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CN105745298A (en) * 2013-11-12 2016-07-06 曙制动器工业株式会社 Friction material composition and friction material
CN106299281A (en) * 2016-08-30 2017-01-04 中盐安徽红四方锂电有限公司 A kind of negative material of low temperature lithium battery and preparation method thereof

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CN105745298A (en) * 2013-11-12 2016-07-06 曙制动器工业株式会社 Friction material composition and friction material
CN106299281A (en) * 2016-08-30 2017-01-04 中盐安徽红四方锂电有限公司 A kind of negative material of low temperature lithium battery and preparation method thereof

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